US3876631A - Process for the preparation of nitrogen-containing derivatives of acids - Google Patents

Process for the preparation of nitrogen-containing derivatives of acids Download PDF

Info

Publication number
US3876631A
US3876631A US664594A US66459467A US3876631A US 3876631 A US3876631 A US 3876631A US 664594 A US664594 A US 664594A US 66459467 A US66459467 A US 66459467A US 3876631 A US3876631 A US 3876631A
Authority
US
United States
Prior art keywords
peroxide
compound
formula
reaction
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US664594A
Other languages
English (en)
Inventor
Edwin George Edward Hawkins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BP Chemicals Ltd
BP Chemicals UK Ltd
Original Assignee
BP Chemicals Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BP Chemicals Ltd filed Critical BP Chemicals Ltd
Application granted granted Critical
Publication of US3876631A publication Critical patent/US3876631A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles

Definitions

  • ABSTRACT Nitrogen-containing derivatives of alkane-a,w-dioic acids having nitrogen bound to the 12 carbon atom e.g. w-cyano-alkanoic acids and m-carbamoylalkanoic acids, are produced by heating a compound of formula where X and X are divalent aliphatic radicals which may be the same or different.
  • the present invention relates to the production of nitrogen-containing derivatives of alkanoic acids.
  • X and X are divalent aliphatic radicals, which may be the sameor different.
  • Compounds of formula (F) such as compounds 1,1peroxydicyclopentylamine which is a white solid with a melting point of 22-23C.
  • 1,1peroxydicycloheptylamine which boils in the range 120 130C at a pressure of 0.8 mm Hg.
  • 1,1'peroxydicyclohexylamine which is a white solid insoluble in water but soluble in ethanol, which melts at 40 415C and distills at 94 97C at a pressure of 0.4 mm.I-lg. and at 138 140C at a pressure of 12 mm.I-Ig., may be made by reacting together at least one compound having the essential skeletal structure:
  • the free valencies of the carbon atom in the structure (IX) may be satisfied by any group which will be inert under the reaction conditions, i.e., will not enter into reaction with ammonia or hydrogen peroxide.
  • the carbonyl compound may be acyclic or cyclic.
  • carbonyl compound is acyclic examples of suitable groups which may be bound to the free valencies are hydrogen and alkyl, preferably lower alkyl. It is preferred that at least one alkyl group is bound to a free valency of the carbon atom of structure (IX) the ether group being hydrogen or alkyl, to give compounds of formula where R is alkyl and R is hydrogen or alkyl. Prefera- -bly alkyl groups are bound to both free valencies. Specific examples of carbonyl compounds which may be used are acetone, ethyl methyl ketone, and nbutyraldehyde.
  • the compounds .formedbyreaction of a compound of formula (X) with hydrogen peroxide and ammonia are those of formula (11)
  • at least one compound of formula where 'X is a divalent radical may be used.
  • Carbon atoms may be the only atoms in the ring.
  • the cyclic ketone may be for example a ketone with between five and 12 carbon atoms in the ring, would then have 4 11 carbon atoms forming part of the ring.
  • ketones examples include those of formulae R (x11) 82 I e R 6 R84 85 (XIII) where R to R are alkyl groups or hydrogen.
  • R to R are hydrogen or lower alkyl e.g. methyl, ethyl, propyl, but compounds with longer alkyl chains can also be used.
  • R to R are hydrogen or lower alkyl e.g. methyl, ethyl, propyl, but compounds with longer alkyl chains can also be used.
  • Examples of compounds of the above formulae which may be used are those in which not more than one alkyl group is joined to each carbon atom in the ring. Compounds in which two alkyl groups are joined to a single carbon atom may be used, however. When the ring is a six carbon atom ring, then any gem-dialkyl groups are preferably substituted in positions 3,4 or on the ring.
  • ketones which may be used are cyclopentanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 3,3,5-trimethylcyclohexanone (dihydroisophorone), and cycloheptanone.
  • the compounds produced by reaction of a compound of formula (XI) with hydrogen peroxide and ammonia are those of formula (F). Where only one compound of formula (XI) is used, and the radical X is inert under the reaction conditions the radicals X and X in the compound of formula (F) will be the same although the compound of formula (F) may exist in a number of different stereoisomers.
  • 1,1 '-dihydroxydicyclohexyl peroxide can be reacted with ammonia to give 1,1 -peroxydicyclohexylamine.
  • a novel compound of formula (XXII) which may be produced by the process described above is l-amino- 3,3,5-trimethylcyclohexyl hydroperoxide. This compound whose structure was established by nuclear magnetic resonance and infra-red spectroscopy, and by elemental analysis is unstable if kept at temperatures much above C and melts with decomposition at 67 675C.
  • the compound may be made by the process of the present invention using dihydroisophorone as the cyclic ketone U Y Me Me 00H Me NR MeMe
  • Another novel compound which may be made by the process of the present invention is l-amino-4- methylcyclohexyl hydroperoxide which may be made by the process of the present invention using 4-methylcyclohexanone as starting material.
  • compounds of formula (X) may be used, to give products of formula (II) while compounds of formula (XI) give products of formula (F)
  • specific carbonyl compounds which may be used are formaldehyde, acetaldehyde, nbutyraldehyde, acetone, ethyl methyl ketone, diethylketone, acetophenone, cyclopentanone, cycloheptanone, and 3,5,5-trimethylcyclohexanone.
  • All the reactions described above can be carried out without a catalyst, although catalysts can be used, by bringing the reactants into contact. This may be done by mixing the reactants in the liquid phase. Where the reactants are all liquids or gases as may often be the case when carbonyl compounds of structure (IX), hydrogen peroxide and ammonia are being reacted together, simple mixing of the reactants may be sufficient. Where one of the reactants is a solid it may be dissolved in a solvent, which should preferably be miscible with the other constituents of the reaction mixture. Thus when reacting carbonyl compounds with hydrogen peroxide and ammonia the solvent used should be miscible, preferably completely, with hydrogen peroxide and water.
  • hydrogen peroxide is a reactant it will generally be in the form of an aqueous solution.
  • the strength of this solution may vary between moderately wide limits.
  • suitable hydrogen peroxide solutions are those containing between -l00% by weight of the total solution of hydrogen peroxide.
  • commercially available solutions containing about 28-30% by weight of hydrogen peroxide are satisfactory.
  • the reaction mixture may contain a hydrogen peroxide stabiliser e.g. sodium ethylene diamine tetraacetate (LDTA).
  • the concentration of hydrogen peroxide in the reaction mixture in which it is used will depend not only on the strength of the hydrogen peroxide solution added but on the quantities of other reactants and solvents present.
  • the quantity of hydrogen peroxide in the reaction mixture may vary over a wide range. Examples of suitable concentrations of hydrogen peroxide in the reaction mixture are those in the range 540% by weight, particularly suitable concentrations being those in the range 10-20% by weight.
  • the molar ratio of ketone and hydrogen peroxide reacted together may vary over a moderately wide range for example between 4:! and 0.511 but when preparing compounds having the structural unit (I) it is preferred to use at least 2 moles of ketone for 1 mole of hydrogen peroxide, the stoichiometric ratio being 2:1.
  • a molar ratio of ketone to hydrogen peroxide of about 121, this being the stoichiometric ratio for the reaction.
  • ammonia is a reactant it may be fed into the reaction mixture in the form of a gas or as a solution in for example water.
  • concentration of the ammonia solution may vary over moderately wide limits and 0.880 ammonia, i.e., an aqueous solution having a relative density of 0.880, is suitable.
  • the reaction may be started with the ammonia added to the other reactants as a solution and may be continued by passing gaseous ammonia into the reaction mixture.
  • ammonia is a reactant it is preferred to use a slight excess over the stoichiometric quantity but the quantity of ammonia is not critical.
  • temperatures at which the reactions described above may be carried out will depend upon the thermal stability of the reactants and products as the use of temperatures sufficiently high to decompose the reactants and products must be avoided.
  • temperatures which may be used are temperatures in the range 20C to +20C, in particular l0C to +l0C.
  • temperatures in the range 20C to +20C in particular l0C to +l0C.
  • reacting compounds of formula (XI) with hydrogen peroxide and ammonia or compounds of formula (XVII) or (XVIII) with ammonia it may be possible to use a somewhat wider range of temperatures, for example temperatures in the range 20C to +60C, preferably those in the range 0C to 50C. Temperatures of about 40C are often particularly suitable.
  • temperatures in the range 20C to +20C for example temperatures in the range l0C to +10C in particular temperatures below 0C.
  • the duration of the reaction when preparing compounds containing the structural unit (I) will depend upon the temperature and the particular reactants used and may vary over a wide range. The reaction may be complete in 2 to 3 hours but longer time may sometimes be desirable.
  • the peroxide (I) and (XXII) may be recovered in any suitable manner or may be used, without recovery, in further reactions. Where the reaction is carried out in aqueous solution the peroxide of formula (I) will generally separate out as a solid or in a liquid layer from the aqueous solution. Where the peroxide (I) is to be reacted further, this product rich in peroxide (I) can be separated from the reaction mixture and used without further purification. Alternatively the peroxide (I) may be extracted from the reaction using a suitable organic solvent e.g. chloroform, ether, light petroleum, benzene, or ethyl acetate.
  • a suitable organic solvent e.g. chloroform, ether, light petroleum, benzene, or ethyl acetate.
  • the peroxide (I) may then be separated from the extract by distillation, if necessary under reduced pressure, provided that the distillation temperature is not so high as to decompose the peroxide.
  • the compounds according to the present invention are not restricted to those made from carbonylcompounds (IX) carrying groups which are inert under the reaction conditions.
  • the groups bonded to the free valencies shown in structure (I) may well differ from those found in the compounds from which the compound of structure (I) is prepared.
  • ammonia and hydrogen peroxide are reacted together with a carbonyl compound which contains groups which react with ammonia and/or hydrogen peroxide it may often still be possible to obtain compounds containing the structural unit (I) but the groups bonded to the free valencies in the structure (I) will not necessarily then be the same as those bonded to the carbonyl group in the starting material.
  • the perchloric acid equivalents of substances given in the examples were determined by titrating an anhydrous N/ 10 solution of perchloric acid in acetic acid with a solution in acetic acid of a weighed sample of the substance whose equivalent is being determined.
  • the peroxide or active oxygen equivalents of substances given in the examples were determined by adding a saturated solution of potassium iodide (containing a quantity of potassium iodide in excess of that required to react with all the peroxide groups in the substance under investigation), to acetic acid to which a small quantity of sodium bicarbonate is added to generate carbon dioxide.
  • a weighed sample of the substance under investigation is then added, the mixture heated on a boiling water bath for 5 minutes, and then cooled. A little water is then added and the mixture titrated with N/lO sodium thiosulphate solution.
  • EXAMPLE II Ethyl methyl ketone (72 g.), 30% hydrogen peroxide (70 c.c.), ammonium acetate (8 g.) and sodium salt of E.D.T.A. (1.- g.) were mixed and treated with gaseous ammonia as in Example 1. The solution was stored at 0C overnight and then extracted with ether. Distillation of the ethereal extract gave a fraction (46.7 g.),
  • This peroxide was of the type according to the present invention and this example illustrates the production of compounds according to the present invention from carbonyl compounds in which the groups bound to the carbonyl group are not inert.
  • Example II The process of Example I was repeated but using 17.3 g. of 78% pure l-amino-3,3,5-trimethylcyclohexyl hydroperoxide, 30 c.c. of light petroleum and 3 drops of sulpuricacid. The reaction mixture was allowed to stand at 0C for 4 hours and then worked up as in Example I to give the same peroxide product as in Example I (15.4 g.).
  • Butyraldehyde (14.4 g.) was mixed with petrol (b.p. 40 60) (50 cc.) and to the stirred solution at 0 was added l-amino-3,3,5-trimethylcyclohexyl hydroperoxide (17.3 g.; 89% pure). The peroxide dissolved within a few minutes. To the solution were added magnesium sulphate and concentrated sulphuric acid (6 drops) and the mixture stored at 0 overnight. The solution was filtered, the filtrate washed with water, dried and distilled to give unreacted butyraldehyde, dihydroisophorone and a product (11.1 g.), b.p. 85 ll0/1.0 mm. with a peroxide equivalent of 23 1 and a perchloric equivalent of 233. The elemental analysis gave C, 68.6%; H, 11.05%; N, 6.6%. The product was identified as:
  • EXAMPLE XXIV 4-Methylcyclohexanone (50 g.), methanol cc.),- 0.880 ammonia cc.), 30% hydrogen peroxide (355 cc.), and EDTA (0.5 g.) were mixed at room tempera-f ture and the solution saturated with gaseous ammonia.) The mixture was stored for 1 week during which time; a solid product had separated. The product was ex-; tracted with light petrol (b.p. 40 60) to give some insoluble material (6.8 g.), m.p. 79 80(dec.), the 1amino-4-methylcyclohexyl hydroperoxide; peroxide equivalent (active oxygen), 147.5; perchloric acid equivalent 165.
  • the petrol-soluble material was obtained as solid (26.4 g.) m.p. 119- 121; active oxygen equivalent 224; perchloric acid equivalent, 235.
  • the elemental analysis gave C, 70.1% H, 10.5%; N, 6.0%.
  • the LR. and N.M.R. spectra were in agreement with this product being the desired 4,4-dimethyl-l,l peroxy-dicyclohexylamine.
  • the non-crystalline material (9.0 g.) contained unreacted 4-methyl-, cyclohexanone together with further peroxide.
  • Example XXIX The same conditions were used as in Example XXVlll except that after the period of storage the bottom oily layer was separated, dissolved in ethanol, and the ethanolic solution added, with stirring, to water (2 litres). The 1,1-peroxy-dicyclohexylamine separated as solid and filtered off. The yield of slightly wet product was 82 g., redistillation giving 72.6 g. of pure peroxide.
  • EXAMPLE XXXII EXAMPLE XXXIll A mixture of dihydroisophorone (44.9 g.; 0.31 mole), 0.880 ammonia cc.), ethanol cc.) and E.D.T.A. (sodium salt)(0.5 g.) was cooled and ca. 30% hydrogen peroxide (40 cc.; 0.375 mole) added. The stirred mixture was kept at below 0C and ammonia gas passed in. After 6 hours the solid produced was filtered off and the filtrate cooled and retreated with ammonia. Two further crops of solid were obtained. The solid had perchloric acid equivalent of 181 and peroxide equivalent of 164 and elemental analysis gave C, 65.2%; H, 10.9%, N, 7.8%, was washed with water,
  • EXAMPLE XXXIV Dihydroisophorone (44.9 g.; 0.31 mole), 0.880 ammonia (60 cc.), methanol (150 cc.), and E.D.T.A. (sodium salt) (0.5 g.) were mixed and cooled; ca. 30% hydrogen peroxide (40 cc., 0.375 mole) was added, and the stirred, cooled mixture treated with ammonia as above.
  • EXAMPLE XXXV 4-Methylcyclohexanone (50 g.) methanol (120 cc.), 0.880 ammonia (135 cc.), 30% hydrogen peroxide (35 cc.) and E.D.T.A. (0.5 g.) were mixed at room temperature (ca. 20C) and the solution saturated with gaseous ammonia. The mixture was stored for 1 week, during which time a solid product separated. The'product was extracted with light petrol (b.p. 40 60C). Insoluble material (6.8 g.) remained after the extraction. This material had m.p. 79 80(deo.) peroxide equivalent 147.5 and perchloric acid equivalent 165 and was identified as lamino-4-methylcyclohexyl hydroperoxide.
  • EXAMPLE XXXIX EXAMPLE XL l-Aminocyclohexyl hydroperoxide (13.1 g. butyraldehyde (7.2 g.), methanol (25 cc.) and ammonium acetate (1.0 g.) were mixed and stored at 0C overnight. Working up as in Example XXXIX, gave cyclohexanone and butyraldehyde, and a product (8.4 g.), b.p. 89/0.3 mm.
  • each of the radicals -X and X which form part of the rings shown in For-F mula (F) may for example vary from four to 11, i.e., there may be from five to 12 carbon atoms in each ring.
  • Examples of compounds of formula (F) are those compounds where X and X are divalent aliphatic radicals! and four to six of the carbon atoms in each of X and X" form part of the rings. Examples of such compounds are where R to R are alkyl groups or hydrogen.
  • R to R is hydrogen or lower alkyl, e.g. having one to 10 carbon atoms in the chain, in particular those having from one to five carbon atoms in the chain e.g. methyl, ethyl, propyl.
  • the present invention is concerned with the production of derivatives of alkane-a,co-dioic acids in which nitrogen is bound to the w-carbon atom.
  • This nitrogen atom must therefore form part of a nitrogen-containing carboxylic acid derivative e.g. CONH CONH- CO- or CN.
  • the a-carbon atom of the derivative of the alkane-a,wdioic acid may for example form part of a carboxylic acid group or of a derivative of a carboxylic group linked to the nitrogen on the w-carbon atom.
  • Examples 6f derivatives of alkane-a,w-dioic acids having nitrogen bound to the w-carbon atom are decane-l,IO-dicarbonimide which is an example of the imide type of derivative;
  • the peroxyamine fed to the thermal decomposition reaction may be in the form of the pure compound separated from the reaction mixture in which the peroxyamine is formed.
  • Peroxyamine-rich products which can be readily separated from the reaction in which peroxyamine is produced may be used however without further purification.
  • the peroxyamine often separates as an oil layer, containing also unchanged ketone, from the aqueous reaction medium. This oil layer can be fed to the thermal decomposition reaction without isolation of the peroxyamine.
  • the reaction may be carried out in the liquid or vapor phase but if the maximum yield of the alkanea,m-dioic acid derivative is required it is preferred to carry out the reaction in the vapor phase.
  • the preferred temperatures are in the range 300 to 1,000C e.g. temperatures in the range 300C to 600C. Where it is desired to produce the maximum yield of the nitrile-acid derivative it is preferred to use temperatures in the range 400C to 600C.
  • the vapor phase reaction may be carried out in any suitable manner, for example by feeding a solution of the peroxyamine into the top of a heated column, which may be packed with inert material e.g. glass balls and withdrawing the product containing the desired derivatives from the base. It is desirable that the peroxyamines should be heated to the reaction temperature as quickly as possible. This may be achieved by spraying the peroxyamine, either molten or in solution, into gas heated to temperatures in excess of the desired reaction temperature, the gas being cooled to the desired reaction temperatures by vaporisation of the liquid.
  • the pyrolysis may be carried out in an atmosphere of an inert gas, e.g. nitrogen.
  • Any solvent which is inert to the conditions of the pyrolysis reaction may be used for dissolving the peroxide, e.g. ethanol, pyridine, B-picoline, benzene, chloroform, aqueous ethanol, cyclohexanone, tributylamine, ethylene glycol.
  • the solution may be of any desired concentration for example %-100% by weight e.g. 50% 100% by weight peroxide based on weight of solvent.
  • the solvent may in fact form a minor proportion of the mixture, thus mixtures consisting of 90% by weight of the peroxide (F) and 10% by weight of cyclohexanone may be used, the small proportions of cyclohexanone being sufficient to give a liquid mixture.
  • the peroxide may also be fed as a vapour without solvent, e.g. in a stream of inert gas.
  • the principal nitrogen containing derivatives of alkane-a, w-dlOiC acids produced in the vapor phase reaction are imides, nitrile-acids and acid-amides; if 1,1 -peroxydicyclohexylamine is heated in the vapor phase reaction at elevated temperature, the dicarbonimide is decane-l ,IO-dicarbonimide (H), the nitrile acid is 1 l-cyanoundecanoic acid (111) and the acid amide is 1 l-carbamoylundecanoic acid (IV).
  • the skeletal structure of the derivatives produced will depend upon the nature and position of any substituents on the rings of the compound (F) fed to the reactor.
  • the type of derivative produced will depend on the reaction conditions. High temperatures favor the formation of the nitrile acids. At a given temperature the proportion of nitrileacid is increased by increased by increasing the pressure at which the thermal decomposition is carried out, by decreasing the rate of feed to the heated column or by increasing the concentration of peroxide in the solvent, i.e., by increasing the contact time.
  • the vapor phase reaction is rapid and examples of residence times of the peroxyamine which can be used are: 0.1 seconds to 2 seconds.
  • Examples of methods by which the derivative of alkane-a,m dioic acid may be separated from the crude product are distillation and recrystallisation from solvents.
  • the nitrogen-containing alkane-dioic acid derivatives produced in the thermal decomposition step such as w-carbamoyl-alkanoic acids and co-cyano-alkanoic acids may be converted to m-amino-alkanoic acids which are useful in the production of polyamides by hydrogenating them or their alkali metal salts, in the presence of a hydrogenation catalyst.
  • the mixture of thermal decomposition products may be separated into its components which may be hydrogenated separately, or the mixture may be hydrogenated without being separated into its components.
  • alkali metal salts of the nitrogen-containing alkane-dioic acid derivatives can be formed, these may be used in the hydrogenation reaction giving the corresponding alkali metal salts of the w-amino-alkanoic acid.
  • alkali metal salts of w-carbamoyl-alkanoic acids and w-cyanoalkanoic acids may be used.
  • the hydrogenation to give l-aminododecanoic acid is carried out in the presence of a hydrogenation catalyst.
  • a hydrogenation catalyst for example (a) platinum catalysts in particular in the form of the finely divided metal e.g. Adams catalyst (b) palladium catalysts e.g. palladium on charcoal catalysts (c) rhodium catalysts.
  • Other hydrogenation catalysts which may be used are the mixed noble metal catalysts e.g. rhodium-platinum, rhodium-palladium, rhodium-ruthenium, and ruthenium palladium catalysts and nickel and cobalt catalysts e.g. Raney catalysts.
  • the reaction may be carried out in the liquid phase by mixing the material to be hydrogenated with a solvent.
  • the solvent will conveniently be acetic acid when using noble metal hydrogenation catalysts and aqueous alcoholic or aqueous-alcoholic ammonia when using Raney nickel or cobalt catalysts.
  • the catalyst is also intimately mixed with the solution which is then brought into intimate contact with the hydrogen. This may be conveniently done by bubbling hydrogen through the solution or by agitating the solution in a hydrogen atmosphere.
  • the optimum temperature and pressure for the hydrogenation will depend upon the catalyst used. When noble metal catalysts are used the hydrogenation is conveniently carried out at room temperature e.g. between 10C 25C and at atmospheric pressures. When nickel and cobalt hydrogenation catalysts are used temperatures between 10C and 200C and pressures between 1 and 300 atmospheres may be conveniently used. The duration of the reaction will of course depend upon the reaction conditions and reaction times may be 5 hours or more and as short as 20 minutes or less.
  • the w-amino-alkanoic acid produced in the hydrogenation reaction may be recovered in any convenient manner.
  • a noble metal catalyst in acetic acid the catalyst is filtered off, the solvent evaporated to give the amino-acid, which may then be recrystallised, if required, from e.g. a large volume of water.
  • Raney nickel or cobalt catalysts in an ammoniacal medium the amino-acid is largely precipitated on the catalyst, and may be extracted from the catalyst with a solvent e.g. acetic acid and/or hot water. Any amino-acid in the ammoniacal solvent in which the hydrogenation was carried out will be in the form of the ammonium salt.
  • the acid may be liberated by neturalisation or by evaporating off the ammonia.
  • EXAMPLE 2 A peroxide was prepared by reacting together 4-methylcyclohexanone, hydrogen peroxide, and ammonia. The resulting peroxide, 4,4-dimethyl-l,l peroxydicyclohexylamine (g.) was dissolved in ethanol (60 cc.) and the solution dropped through the heated column as in Example 1 at 400 and a pressure of 150 mm. in 45 minutes. Part of the peroxide had not reacted, so that the product, after evaporation of the ethanol, was redissolved in benzene (20 cc.) and the solution dropped through the same column in 1 hour.
  • EXAMPLE 8 1,1-Peroxydicyclohexylamine (8 g.) dissolved in ethanol (40 c.c.) and pyridine (l c.c.) was fed to the reactor used in Example 5 through which a slow stream of nitrogen was passed at a temperature and pressure of 500 and 150 mm. respectively during 30 minutes. Distillation gave a caprolactam fraction 0.8 g.), a fraction (5.7 g.) containing ll-cyanoundecanoic acid (82% by titration) as well as caprolactam, and a residue (0.3 g.).
  • EXAMPLE 1 l 1,1'-Peroxydicyclohexylamine (10 g.), dissolved in chloroform (20 c.c.) was fed to the reactor used in example 5 through which a slow stream of nitrogen was passed at a temperature and pressure of 440 and 15 mm. respectively during 35 minutes. Solvent was evaporated from the product, the residue treated with light petroleum, the solution cooled and imide (5.6 g.) filtered off. The filtrate was evaporated and residue distilled to give cyclohexanone (0.7 g.), a caprolactam fraction (0.9 g.), and a fraction (1.6 g.) containing mainly ll-cyanoundecanoic acid with some 11- carbamoylundecanoic acid.
  • EXAMPLE 14 1,1Peroxydicyclohexylamine (8 g.) dissolved in a mixture of ethylene glycol g.) and ethanol (8 c.c.) was fed into the reactor used in Example 5 through I which a slow stream of nitrogen was passed at a temperature and pressure of 440 and 15 mm. respectively during 40 minutes. The product was diluted with chloroform, washed with water to remove glycol and ethanol, the chloroform solution evaporated and petrol added to the residue.
  • caprolactam by gasliquid chromatography
  • EXAMPLE l6 1,1'-Peroxydicyclohexylamine (14.8 g.) was distilled under nitrogen through a 21 in. long empty glass reactor heated by a furnace to a temperature of 500. The pressure inside the system was 0.1 mm.
  • the product (14.7 g.) was shown to contain 8.6 g. of 11- cyanoundecanoic acid, 1.7 g. od caprolactam and 1.9 g. of cyclohexanone.
  • EXAMPLE 17 The process of Example 15 was repeated but using instead of solid 1,1'-peroxydicyclohexylamine, a portion (16 g.) of the oil of which had separated from the aqueous layer when aqueous hydrogen peroxide, cyclohexanone, ammonia, were reacted together for 2 hours.
  • the 16 g. of oil contained 14.2 g. of l,l'-peroxydicyclohexylamine.
  • the product remaining after removal of the ethanol solvent weighed 13.6 g. and contained 11- cyanoundecanoic acid (7.8 g.), caprolactam (1.8 g.)
  • EXAMPLE 18 1,1'-Peroxydicyclohexylamine (8 g.) in pyridine g.) containing Triton B (Triton B is benzyl trimethyl ammonium hydroxide)(0.l c.c. of a 40% aqueous solution) was heated under reflux at atmospheric pressure for 12% hours. Distillation of the mixture, which still contained 20% unreacted peroxide gave, in addition to pyridine and cyclohexanone, a fraction (2.0 g.), b.p. /l5 mm., containing 40% caprolactam together with the peroxide; and a fraction (2.6 g.), b.p. 155 270 at 15 mm. containing the C acid-amide (l l-carbamoylundecanoic acid).
  • Triton B is benzyl trimethyl ammonium hydroxide
  • a process for the production of a derivative of an alkane-a,w-dioic acid having nitrogen bound to the w-carbon atom which comprises heating a compound of the formula wherein R to R are lower alkyl of one to 10 carbon atoms or hydrogen, in the vapor phase at a temperature of from about 300 C. to about 1,000 C.
  • the solution is a solution in methanol, ethanol, cyclohexanone, pyridine, a pyridine base, chloroform, benzene, ethylene glycol or aqueous ethanol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Hydrogenated Pyridines (AREA)
  • Cephalosporin Compounds (AREA)
US664594A 1966-08-12 1967-08-11 Process for the preparation of nitrogen-containing derivatives of acids Expired - Lifetime US3876631A (en)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB3610766 1966-08-12
GB10070/67A GB1198422A (en) 1966-08-12 1966-08-12 Process for the preparation of Nitrogen-Containing Derivatives of Acids
GB4275666 1966-09-24
GB4697166 1966-10-20
GB5032466 1966-11-09
GB1007167 1967-03-03

Publications (1)

Publication Number Publication Date
US3876631A true US3876631A (en) 1975-04-08

Family

ID=27546634

Family Applications (2)

Application Number Title Priority Date Filing Date
US664594A Expired - Lifetime US3876631A (en) 1966-08-12 1967-08-11 Process for the preparation of nitrogen-containing derivatives of acids
US04/667,061 Expired - Lifetime US3947406A (en) 1966-08-12 1967-09-12 Process for the production of lactams

Family Applications After (1)

Application Number Title Priority Date Filing Date
US04/667,061 Expired - Lifetime US3947406A (en) 1966-08-12 1967-09-12 Process for the production of lactams

Country Status (8)

Country Link
US (2) US3876631A (fr)
AT (2) AT286956B (fr)
BE (2) BE702603A (fr)
CH (2) CH512440A (fr)
ES (2) ES344030A1 (fr)
GB (1) GB1198422A (fr)
NL (2) NL6711091A (fr)
SE (1) SE355355B (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4971914A (en) * 1984-12-11 1990-11-20 Litmus Concepts, Inc. Developer for fecal occult blood tests
US5053342A (en) * 1987-12-24 1991-10-01 Litmus Concepts, Inc. Fecal occult blood test reagents
US5076966A (en) * 1990-07-02 1991-12-31 John J. McSheffrey Composition and method for testing smoke detectors
CN114933548A (zh) * 2022-05-30 2022-08-23 江苏扬农化工集团有限公司 一种由1,1’-过氧化双环己胺热解氨化生产十二烷二腈的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1309137A (en) * 1970-09-07 1973-03-07 Bp Chem Int Ltd Production of 11-cyanoundecanoic acid

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1412979A (fr) * 1964-11-02 1965-10-01 Inventa Ag Procédé pour la préparation d'acides omega-cyanocarboxyliques aliphatiques
GB1094273A (en) * 1965-05-31 1967-12-06 Grace W R & Co Adipimide derivatives

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3000879A (en) * 1961-09-19 Process for the production of

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1412979A (fr) * 1964-11-02 1965-10-01 Inventa Ag Procédé pour la préparation d'acides omega-cyanocarboxyliques aliphatiques
GB1094273A (en) * 1965-05-31 1967-12-06 Grace W R & Co Adipimide derivatives

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4971914A (en) * 1984-12-11 1990-11-20 Litmus Concepts, Inc. Developer for fecal occult blood tests
US5053342A (en) * 1987-12-24 1991-10-01 Litmus Concepts, Inc. Fecal occult blood test reagents
US5076966A (en) * 1990-07-02 1991-12-31 John J. McSheffrey Composition and method for testing smoke detectors
CN114933548A (zh) * 2022-05-30 2022-08-23 江苏扬农化工集团有限公司 一种由1,1’-过氧化双环己胺热解氨化生产十二烷二腈的方法
CN114933548B (zh) * 2022-05-30 2023-07-25 江苏扬农化工集团有限公司 一种由1,1’-过氧化双环己胺热解氨化生产十二烷二腈的方法

Also Published As

Publication number Publication date
NL6713008A (fr) 1968-03-25
US3947406A (en) 1976-03-30
NL6711091A (fr) 1968-02-13
BE702603A (fr) 1968-02-12
DE1643640A1 (de) 1971-10-14
ES344030A1 (es) 1968-11-01
CH512440A (fr) 1971-09-15
CH476660A (fr) 1969-08-15
SE355355B (fr) 1973-04-16
GB1198422A (en) 1970-07-15
DE1643640B2 (de) 1976-02-26
AT284807B (de) 1970-09-25
ES345390A1 (es) 1969-01-16
BE704214A (fr) 1968-03-22
AT286956B (de) 1971-01-11

Similar Documents

Publication Publication Date Title
HU207284B (en) Process for producing 1-amino-methyl-1-cyclohexane-acetic acid
Rastetter et al. 3, 5-Dinitroperoxybenzoic acid. A crystalline, storable substitute for peroxytrifluoroacetic acid
US3876631A (en) Process for the preparation of nitrogen-containing derivatives of acids
US3397223A (en) Preparation of cyclopropane derivatives
Ohno et al. Reactions of 2-Chlorocycloalkanone Oximes. II. Syntheses of 3-Aminocycloalka [C] isoxazoles
US2601224A (en) Preparation of difunctional compounds
US3988319A (en) Process for producing caprolactam from 6-aminocaproic acid
US3223712A (en) Synthesis of thioctic acid and thioctic acid amide
US3652549A (en) Production of epsilon-caprolactam
Torra et al. N-nitrosation and N-nitration of lactams. From macrolactams to macrolactones
US5254711A (en) Continuous preparation of 3-cyano-3,5,5-trimethylcyclohexanone
US3891663A (en) Peroxy compounds and processes for their preparation
US3585188A (en) Process for producing 2'-deoxyuridine
US4058563A (en) Novel schiff bases
US3983142A (en) Peroxy compounds and processes for their preparation
JPH0678304B2 (ja) Ｎ−アルキル置換ラクタムの製造方法
Stevens et al. gem-Dihalides from the Hofmann Degradation of α-Haloamides1
US2937201A (en) Process for the production of azelaic acid
US3983131A (en) Process for the production of 1,1'-peroxydicyclohexylamine
US3422132A (en) Preparation of primary alpha-aminonitriles
US4010160A (en) Process for the manufacture of 1,3-bis-(β-ethylhexyl)-5-amino-5-methyl-hexahydropyrimidine
US4009209A (en) Dimerization of cyclohexylidene-acetonitrile and hydrogenation of the resulting substituted glutaric acid dinitrile
Cramer et al. Isoxazole Derivatives from Acetylene and Nitrogen Oxides
EP0632004B1 (fr) Procédé pour la préparation de cétones cycliques
US3019264A (en) 2-(2, 2, 3-trimethylcyclobutyl)-hepta-2, 4-dien-6-one